JPS63289058A - Colored polycarbonate composition - Google Patents

Abstract

PURPOSE:To obtain the title composition protected from deterioration of hue by diffusion of a colorant and excelling in optical properties, solvent solubility, antistatic property and heat resistance, by mixing a specified colorant with at least two polycarbonates. CONSTITUTION:A colorant which generates charges by absorption of a light (e.g., Rhodamine B) is kneaded with a polycarbonate of a glass transition temperature of 100-200 deg.C, a number-average MW of 5,000-100,000 and an acid number of 5-60mgKOH/g and a polycarbonate of an acid value of 0-4mgKOH/g and having an affinity for said colorant different from that of the former polycarbonate.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a colored polycarbonate composition that is uniformly colored, and in particular prevents deterioration of various properties caused by colorants such as bleed-out, and The present invention relates to a uniformly colored polycarbonate composition that does not affect the hue of each colorant even when a plurality of resin compositions using colorants are mixed.

[Conventional technology]

2. Description of the Related Art Conventionally, thermoplastic polymers such as acrylic polymers and polyesters have been widely used in various fields because they have excellent mechanical properties, moldability, and optical properties such as transparency. Many of these fields of application require coloring.

On the other hand, in recent years, coloring agents have also been understood by the concept of pigments from a so-called academic point of view, and for this reason, colorants have been considered as dyes,
Applications that utilize not only the color of colorants such as pigments, food colors, and cosmetic dyes, but also use the physical and chemical properties inherent in colorants such as dye lasers, dye semiconductors, and liquid crystals. Its uses are gradually increasing.

From this perspective, dispersing colorants (dyes) in various dispersion forms into polymeric compounds with excellent mechanical properties and moldability is an effective way to extract the functions of these colorants (dyes). It has become an important technology for this purpose.

[Problem that the invention seeks to solve]

It is desirable that the coloring of such a polymer compound be as simple as possible, such as simply mixing and kneading the colorant and the polymer compound.

However, when a colorant is simply blended into a thermoplastic polymer, a mottled pattern is likely to occur due to non-uniform dispersion, and in extreme cases, bleeding may occur on the surface. In addition, the presence of colorants may affect the inherent properties of thermoplastic polymers, such as surface properties such as charging properties, paintability,
Chemical resistance etc. may be significantly reduced, and the practicality of the colored resin composition may be lost.

As a result of our intensive research, we attempted to solve the problems of coloring thermoplastic polymers, namely uneven dispersion such as mottled patterns and deterioration of surface properties, all at once.
Since the conventional technology was improved solely for the purpose of uniformly dispersing the coloring agent into the polymer compound, there was a recognition that attempts were made to form a colored composition that formed a complex between the colorant and the polymer. We believe that this is because the colorant was not introduced and the location where the colorant was introduced was not controlled.
In order to clearly distinguish between the functions of the colorant and the function of the thermoplastic polymer, we previously proposed a solution to the above problem by allocating both functions to the matrix (continuous phase) and dispersed phase in the composition. (Special application No. 60-233042,
62-70868).

That is, we have proposed a colored acrylic polymer composition comprising a colorant and two or more similar resins, such as polyesters or styrenic polymers, having different affinities with the colorant.

However, with polyester and styrene polymers,
For example, when used in an organic photoreceptor for electrophotography, it has drawbacks such as difficulty in imparting a surface charge (positive chargeability) and low heat resistance.

[Means for solving problems]

Therefore, it is absolutely necessary to improve electrical properties and heat resistance while maintaining optical properties and solvent solubility.
The present invention achieves this objective by using a specific coloring agent and the same polycarbonate.

That is, the present invention is a colored polycarbonate composition characterized by blending a coloring agent that generates electric charges by light absorption and two or more types of polycarbonates having different affinities with the coloring agent.

[Detailed description of the invention]

A. Components The colored polycarbonate composition of the present invention basically consists of a colorant and two or more polycarbonates having different affinities with the colorant.

1. The coloring agent used in the present invention is required to have the properties described in the coloring section.

i) It has the property of penetrating into either the dispersed phase or the polycarbonate forming the matrix, that is, the affinity for the polycarbonate of either the polycarbonate forming the matrix or the polycarbonate forming the dispersed phase, Preferably, the colorant is larger than that for the other polycarbonate.

If the colorant itself does not have the above properties, it may be treated with other components to impart the above properties.

ii) The particle size (average dispersion diameter) of the colorant is smaller than the size of the dispersed phase when the colorant enters the dispersed phase.

iii) The colorant has the property of generating electric charge by absorbing light.

It is important that the coloring agent used in the present invention has the above-mentioned properties.When coloring, it is necessary to use the coloring agent as long as it does not change the color to a hue other than the intended one or cause unfavorable changes in the properties of the resin. can do. Specifically, basic dyes such as rhodamine B, acid dyes, fluorescent dyes,
In addition to ab-based dyes such as chlorodiampurus, anthraquinone dyes, azine dyes, and metal complex compound dyes, phthalocyanine pigments such as copper phthalocyanine, zinc phthalocyanine, and metal-free phthalocyanine, copper naphthalocyanine,
Naphthalocyanine pigments such as nickel naphthalocyanine, perylene pigments, perinone pigments, polycyclic quinone pigments, indigo pigments, thioindigo pigments, azo lake pigments, squarylium pigments,
Pyrylium-based, quinacridone-based, cyanine-based, cadmium yellow, cadmium red, basic dye lake, medium ≠ mocking → = hard, so preferred.

Polycarbonate The polycarbonate used in the present invention is an aromatic polycarbonate, in which at least the majority of the dihydroxy compounds constituting the ester of carbonic acid have two phenolic hydroxyl groups. Specifically, there are bisphenols, especially bisphenol A.

Aromatic polycarbonate is made by combining the above-mentioned "dihydric phenol" with a carbonate precursor, ie, phosgene,
It is produced by reacting with bischloroformate, carbonic acid diester, etc.

Polycarbonates that exhibit the effects of the present invention are:
The glass transition temperature is 100°C to 200°C, especially 1
A temperature of 20° C. to 170° C., and a number average molecular weight of 5,000 to 100,000, particularly 6,000 to 50,000, are highly effective. In addition, from a practical point of view when the composition of the present invention is applied to the fields of coating agents such as paints, thin film materials, binders, etc., non-quality materials with a crystallinity of less than 5% as determined by X-ray analysis, especially Solvent-soluble ones are preferred.

One of the features of the present invention is that the coloring agent is contained in the components constituting the dispersed phase or matrix. That is, the affinity of the colorant for either the matrix or the dispersed phase is large, and the interaction between the matrix, the dispersed phase, and the colorant is important. For example, in the colored polycarbonate composition of the present invention, it is necessary that the colorant remains in the dispersed phase or matrix, not to mention in the solid state at room temperature, but even after undergoing thermal history and passing through the molten state. In other words, it is important that the colorant is prevented from diffusing into the matrix or dispersed phase.

In order for the colorant to remain in the dispersed phase and not diffuse into the matrix, the electric attraction between the matrix polycarbonate (M) and the colorant (C) must be It is desirable to select each polycarbonate in such a way that the electrical attractive force between the polycarbonate and the agent (C) is large. Also,
In order to keep the colorant in the matrix and prevent it from diffusing into the dispersed phase, it is desirable to select a polycarbonate that has the opposite electrical attraction relationship as described above.

In order to make the electrical properties of the matrix polycarbonate (M) and the dispersed phase polycarbonate (D) different, a functional group for expressing predetermined electrical properties may be introduced into either one, or both. It is desirable to introduce functional groups to exhibit contradictory electrical properties. Such a material can be selected, for example, by combining a polycarbonate with a high acid value and a polycarbonate with a low acid value. If such polycarbonates already exist, selections can be made from such existing polycarbonates.

As polycarbonate having such functional groups,
For example, unsaturated organic acids, their alkyl esters, or their anhydrides (
Specifically, unsaturated organic acids such as unsaturated aliphatic monocarboxylic acids such as acrylic acid, methacrylic acid, and α-ethyl acrylic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; There are acrylic copolymers (including graft copolymers) containing the alkyl ester or anhydride) as a comonomer. Examples of substances with positive electrical properties include vinyl monomers having amino groups or amide groups, or quaternized salts thereof (specifically, N,N-dimethylaminoethyl methacrylate, N
, N-diethylaminoethyl methacrylate, N-ethyl-N-phenylaminoethyl methacrylate, N,N
-dimethylaminopropylmethacrylamide, N,N-
There are polycarbonate copolymers (including graft copolymers) containing diethylaminoethylmethacrylamide, vinylpyridine, vinylpiperidine, etc.) as comonomers.

There is also a method of introducing a functional group by utilizing a reaction with the terminal group of a molecular chain.For example, in the present invention, in order to generate an acid terminal, a commercially available polycarbonate with a low acid value and a dicarboxylic acid such as an aromatic dicarbonate are used. Polycarbonate with a high acid value can be obtained by melt-kneading it with the acid terephthalic acid or its monometallic salt at high temperature.

A suitable combination of a colorant and a polycarbonate that has a different affinity for these colorants is one in which the colorant has positive electrical properties, more specifically, one in which it has positive chargeability, and the measured value is The colorant is preferably negative or non-zero and exhibits a measured value of 5) 1c/g (microcoulombs/gram) or more.

The positive chargeability mentioned here refers to the blow-off method, which is a charge measurement method for powder (Oguchi et al.: "Electrophotography", 16, 52.1).
977).

On the other hand, polycarbonate has a high acid value, specifically 5 to 60 mgKOH/g, preferably 10 to 30 m
gKOll/g. At this time, the other polycarbonate having a different affinity is one with a low acid value, specifically, 0 to 4 mgKon/g, preferably θ to 3 mgK.
OII/g.

B, Production of Mi oxide/formation of phase structure In the colored polycarbonate composition of the present invention, the dispersed phase is preferably finely and uniformly dispersed in the matrix. In such a uniformly dispersed system, when the polycarbonate containing the colorant and forming the dispersed phase and the polycarbonate constituting the matrix are mechanically blended, their molecular weight, molecular weight distribution, and copolymerization ratio It is formed by appropriately selecting the type of composition of the blend, and the blending conditions such as the equipment, temperature, kneading speed, and kneading time used in the blending, taking these factors into consideration.

Blending conditions that should be considered in particular include the importance of the viscosity and molecular weight of the polycarbonate; it is preferable that the viscosity of the polycarbonate constituting the dispersed phase be higher than that of the matrix polycarbonate; Larger is preferable.

The size of the dispersed phase in the matrix does not need to be particularly limited since both the dispersed phase and the matrix use polycarbonate, but from the viewpoint of maintaining the transparency of the polycarbonate composition, the particle size of the dispersed phase should be 10 μm or less. In particular, it is preferably 5 μm or less. The particle size referred to here is an average particle size (Martin's diameter) measured by observing a cross section of a sample with an electron microscope.

Of the polycarbonates blended, it is a matter of course that the polycarbonate with a relatively larger blending amount is more likely to form a matrix.

When blending the coloring agent, it is preferable to thoroughly knead the coloring agent and the polycarbonate having a higher affinity before blending the polycarbonates together. This controls the diffusion of the colorant into other polycarbonates. It is thought that the strong interaction between one polycarbonate and the colorant changes its compatibility with the other polycarbonate, causing phase separation between the two.

Further, the amount of the colorant added can be arbitrarily changed depending on the purpose. For example, when the colorant is contained only in the dispersed phase, when it is contained only in the matrix, or when two or more types of colorants are blended, some colorants are contained in the dispersed phase and others in the matrix, or You can arbitrarily adjust the shading, etc.

Furthermore, the colored polycarbonate composition of the present invention may contain optional components such as a stabilizer, a crosslinking agent, and an impact modifier within a range that does not significantly impair the effects of the present invention.

C4 Colored Polycarbonate Composition The colored polycarbonate composition of the present invention produced in this way takes advantage of the difference in affinity between the colorant and the polycarbonate to bind the colorant to the matrix polycarbonate, particularly by encapsulating the colorant in the dispersed phase. The influence of the colorant can be prevented, and furthermore, the dispersed phase can be finely and uniformly dispersed to prevent the colorant from being uniformly dispersed.

Moreover, by incorporating a colorant into the matrix, new effects can be obtained by the colorant.

In the colored polycarbonate composition of the present invention, two or more types of polycarbonates are blended, but in the absence of a colorant, it is normal that no microphase separation phenomenon can be observed. However, by blending a specific polycarbonate in combination with a specific colorant, a microphase separation phenomenon can be observed.

〔Example〕

J≧-N*-H decoy-∆ decomposed polycarbonate (manufactured by Mitsubishi Gas Chemical Co., Ltd. "Kneepilon S-2000J"
: Molecular weight approximately 22,000, glass transition temperature 134°C)9
5 parts by weight and 5 parts by weight of terephthalic acid were melt-kneaded at 280° C. in a vented twin-screw extruder while suctioning gas generated from a pentro. The product obtained is - day and night 1
It was dried under reduced pressure at 20"C to obtain polycarbonate (8) having an acid value of 15 KOII mg/g.

Example 1 20 parts by weight of the above polycarbonate (A) and 20 parts by weight of stearate-treated copper phthalocyanine were melt-kneaded at 280°C in a vented twin-screw extruder. 40 parts by weight of this melt-kneaded material and polycarbonate (B) (manufactured by Mitsubishi Gas Chemical Co., Ltd. "Nipilon S-2000J: acid value 1 mg
A colored polycarbonate composition (1) was obtained by melt-kneading 60 parts by weight of KO1l/g or less) at 280°C in a vented twin-screw extruder.

Observation of microphase separation: This colored polycarbonate composition (1) was sandwiched between a slide glass and a cover glass, heated and melted on a hot press to form a thin film, and this thin film was observed using a transmission optical microscope. The formation of a dispersed phase was observed, the particle size of which was approximately 0.5 μm, and was uniformly and finely dispersed in the matrix.

Moreover, the colorant was contained in the dispersed phase.

Evaluation of the obtained colored polycarbonate composition (1) was heated by hot pressing to a size of 4.5 cm x 4.5 cm x Q.
The film was formed into a 2In film, and its surface charge retention ability was evaluated using a charge attenuation measuring device (Scitch Honest Meter, manufactured by Shishido Electrostatic Co., Ltd.). The measurement conditions at this time were: applied voltage (-) 10kV, applied electrode height 20cm, receiving height 2On, and measured the time (seconds) until the charged voltage attenuated by half and the attenuation rate after 3 minutes. did. As a result, the sample had a charging voltage of 2.66 kV, a half-life of 180 seconds or more, and a decay rate of 1.8%, indicating good surface charge retention.

Evaluation of heat resistance The heat distortion temperature of colored polycarbonate composition (I) is
The temperature was 138°C, which is the same as Lf measured according to TM-0648 (4.6 kg/cm'' load).

The polycarbonate (8) and polycarbonate I~(B
), the same melt-kneading process was performed except that no colorant was added, and the polycarbonate composition was observed using the same evaluation method as described above. As a result, so-called microphase separation could not be observed.

80 parts by weight of the polycarbonate (A) and 20 parts by weight of the coloring agent used in Example 1 were heated to 280 parts by weight in a vented twin-screw extruder.
A polycarbonate composition in which a colorant was dispersed in one type of polycarbonate was obtained by melt-kneading at a temperature of .degree. This was formed into a sheet in the same manner as in Example 1, and its surface charge retention ability was evaluated. As a result, the charged voltage was 2.39kV
, halved! The tI was 1156 seconds, the decay rate was 54%, and the surface charge retention ability was poor.

Further, when this product was observed for microphase separation in Example 1, no phase separation was observed and the colorant was non-uniformly dispersed.

In Example 1, polycarbonate resin (A) was replaced with polyester (A) (unqualified saturated polyester: glass transition temperature 62°C, acid value 55 KOII mg/g, hydroxyl value 1).
．． 0 KOIImg/g, number average molecular weight approximately 4000)
Also, the polycarbonate resin (B) was replaced with polyester (B) (unqualified saturated polyester: glass transition temperature 51.1°C, acid value 2.OKOII+wg/g, hydroxyl value 40KOIImg/g, molecular weight approximately 3000). A colored polyester was obtained in the same manner as above, except that the melt-kneading temperature was 140°C.

When the surface electrical properties of this material were evaluated, the charging voltage was 4.
00 V, the half-life was 96 seconds, and the decay rate was 67%, which was poor.

In addition, as a measure of heat resistance, we measured the heat distortion temperature and found that it was 4.
f55°C.

〔Effect of the invention〕

In the colored polycarbonate composition of the present invention, by blending two or more types of polycarbonates with different affinities with the colorant, the colorant strongly interacts with the polycarbonate with high affinity, and as a result, the polycarbonates Microphase separation occurs between the polycarbonate and the colorant is inhibited from being diffused into the other polycarbonate,
Deterioration of hue due to colorant diffusion and deterioration of surface properties, especially charging properties of the colored polycarbonate composition are prevented, and a composition with good heat resistance can be obtained. Such effects are extremely important, especially when used as color toners and photoreceptors for electrophotography, and they prevent deterioration of color tone due to toner bleed-out in electrophotographic color copying and reduce the surface charge retention ability of organic photoreceptors. It is extremely useful industrially because it has advantages such as prevention of.

Claims (4)

[Claims] (1) A colored polycarbonate composition comprising a colorant that generates electric charge by light absorption and two or more types of polycarbonates having different affinities with the colorant. (2) The colored polycarbonate composition according to claim 1, wherein a polycarbonate having high affinity is present as a dispersed phase. (3) The colored polycarbonate composition according to claim 1 or 2, wherein the difference in affinity is a difference in acid value. (4) The colored polycarbonate composition according to any one of claims 1 to 3, wherein the colorant is a positively chargeable powder.